JP5876182B1 - Curable resin composition, dry film and cured product thereof, and printed wiring board having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain a high level of various properties required for resists such as an etching resist and a solder resist, such as toughness and electrical properties, with excellent adhesion to a low profile substrate. A curable composition, a dry film and a cured product thereof, and a printed wiring board having the same are provided. A curable resin composition comprising (A) an alkali-soluble resin, (B) at least one of a photobase generator and a photopolymerization initiator, and (C) a thermosetting compound having an oxazolidone ring. As a result, a dry film and a cured product thereof, and a printed wiring board having the same were obtained. [Selection figure] None

Description

  The present invention relates to a curable resin composition, particularly a curable resin composition that is suitably used as a resist such as a solder resist.

  Furthermore, this invention relates to the dry film and hardened | cured material of the said curable resin composition, and a printed wiring board which has this.

  Currently, from printed wiring boards for consumer use and industrial printed wiring boards (solder resist, etching resist), from the viewpoint of high accuracy and high density, images are formed by developing after UV irradiation, and heat and light irradiation. A liquid development type photoresist that is finish-cured (mainly cured) at least on the other side is used.

  Among liquid development resists, an alkali development type using a dilute alkaline aqueous solution as a developing solution has become the mainstream in consideration of environmental problems, and is used in large quantities in the production of printed wiring boards. Further, the photoresist is required to have good adhesion to the substrate in addition to toughness and excellent electrical characteristics.

  One method of improving adhesion is to roughen the substrate (copper foil, etc.) by chemical polishing before applying the composition or film to the substrate, thereby increasing the surface area, thereby increasing the anchor effect. The technology to have is widely used. This improves the adhesion between the resist composition or dry film and the substrate. On the other hand, fine pitches are rapidly progressing in response to the increase in the density of printed wiring boards accompanying the downsizing of electronic equipment. Since the fine pitch substrate is also a small thin layer, in order to obtain complete electrical performance, so-called low profile that suppresses irregularities in roughening is also progressing (for example, patents) Reference 1).

  In recent years, there is a tendency for the temperature applied to the package to become very high, such as the transition to surface mounting and the use of lead-free solder in consideration of environmental problems. Along with this, the temperature reached inside and outside of the package is remarkably increased, and the conventional liquid photosensitive resist is improved due to the problem that the coating film cracks due to thermal shock or peels off from the substrate or sealing material. It has been demanded.

In order to solve such a problem, Patent Document 2 includes (A) a carboxyl group-containing resin (however, excluding a carboxyl group-containing resin starting from an epoxy resin),
There has been proposed a photocurable thermosetting resin composition that can be developed with a dilute alkaline aqueous solution, which contains (B) a photopolymerization initiator and (C) an epoxidized polybutadiene.

JP 2008-285751 A JP 2010-256728 A

  However, in Patent Document 1, a low profile of a small thin layer substrate is required. However, the etching rate is also reduced at the roughened level of the low profile, and the resist composition and the substrate are obtained only by the anchor effect. Adhesiveness with is not always obtained sufficiently.

  However, in patent document 2, when the temperature range concerning a package is wide, the said characteristic cannot be said to be fully satisfied, but there was room for the further improvement.

  The object of the present invention is particularly required for a resist, particularly a solder resist for a package, having excellent adhesion to a low profile substrate without providing an additional layer such as a primer layer. An object of the present invention is to provide a curable composition, a dry film and a cured product thereof, and a printed wiring board having the same, which can maintain various characteristics such as toughness and electrical characteristics at high levels.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-described problems can be solved by adopting the following configuration, and have completed the present invention.

That is, the curable resin composition of the present invention is
(A) an alkali-soluble resin,
(B) a photobase generator, and at least one of photopolymerization initiators, and (C) a thermosetting compound having an oxazolidone ring,
It is characterized by containing.

The curable resin composition of the present invention may further contain (D) a block copolymer.
The (D) block copolymer has the following formula (I)
X-Y-X or X-Y-X '(I)
(In the formula, X or X ′ is a polymer unit having a glass transition point Tg of 0 ° C. or more, and Y is a polymer unit having a glass transition point Tg of less than 0 ° C.)
It is preferable to be represented by

  Further, it is more preferable that a polar group is contained in X or X ′ of the (D) block copolymer.

  Furthermore, it is preferable that the weight average molecular weight of (D) block copolymer shall be 10,000-500,000.

  (A) The alkali-soluble resin is preferably at least one of a carboxyl group-containing resin and a phenolic hydroxyl group-containing resin.

  Furthermore, it is preferable that the curable resin composition of this invention contains (E) reactive diluent.

  In the present invention, a dry film is obtained by applying and drying the curable resin composition on a film, and a cured product is obtained by thermally curing the dry film after light irradiation. Further, a printed wiring board having this cured product is manufactured.

  With the curable resin composition of the present invention, it has high adhesion to a substrate such as a low profile copper foil, and has a glass transition point (Tg), thermal expansion coefficient (CTE) and TCT (thermal cycle test) resistance. In addition to excellent physical properties such as high toughness and resolution, a resist having good electrical properties such as insulation resistance is formed. Furthermore, since the curable resin composition of the present invention can be developed with an alkali, it is possible to form a pattern with a developer having a small environmental load.

  The curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) at least one of a photobase generator, and a photopolymerization initiator, and (C) a thermosetting compound having an oxazolidone ring. And

The curable resin composition of the present invention (hereinafter also simply referred to as a composition) is extremely excellent adhesion to both a metal such as a copper foil used as a substrate of a printed wiring board and a plastic material such as polyimide. Have sex. This is an effect brought about by all the components of the composition of the present invention, but in particular, by using a thermosetting compound having (C) oxazolidone ring which is a kind of isocyanate-modified skeleton, In this state, it has extremely excellent adhesion and toughness. Furthermore, when a thermosetting compound, especially an epoxy resin is used, a highly tough film is formed due to the reaction rate with the epoxy resin. The reaction rate is preferably 90% or more, and more preferably 95% or more.
Furthermore, the composition of the present invention is further improved in TCT (thermal cycle test) resistance (by adding a block copolymer).

In particular, the composition of the present invention has the following formula (I) as (D) block copolymer:
X-Y-X or X-Y-X '(I)
(Wherein X or X ′ is a polymer unit (hard segment) having a glass transition point Tg of 0 ° C. or higher, and Y is a polymer unit (soft segment) having a glass transition point Tg of less than 0 ° C.) (D) It is preferable to contain a block copolymer.

  Furthermore, among them, when the polar segment is contained in the hard segment (X or X ′) of the (D) block copolymer, the compatibility with the thermosetting compound (C) having an oxazolidone ring is improved. Since a uniform composition is obtained, high toughness and high adhesion as a cured film are also obtained uniformly throughout the film, which is more preferable.

  Hereinafter, each component of the curable resin composition of the present invention will be described in detail.

[Component (A): Alkali-soluble resin]
In the present invention, an alkali-soluble resin is used as the component (A). (A) As the alkali-soluble resin, at least one of a carboxyl group-containing resin and a phenolic hydroxyl group-containing resin is preferably used. By using the alkali-soluble resin, it is possible to pattern-form the coating film formed from the curable resin composition through development.

  As the carboxyl group-containing resin, various known carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting alkali developability can be used. In particular, when the curable resin composition is a curable resin composition having photosensitivity, the carboxyl group-containing photosensitive resin having an ethylenic double bond in the molecule is more preferable in terms of curability and development resistance. preferable. The ethylenic double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.

  In addition, when using only the carboxyl group-containing resin which does not have an ethylenic double bond, in order to produce the sequential reaction with respect to the ethylenic double bond of a photoinitiator in a composition, as a reactive diluent mentioned later A compound having a group containing an ethylenic double bond in the molecule, that is, a photopolymerizable monomer may be used in combination.

  As specific examples of the carboxyl group-containing resin, the following compounds (any of oligomers and polymers) are preferable.

(1) A carboxyl obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, C ₁ -C ₆ alkyl (meth) acrylate, and isobutylene Group-containing resin.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate polyols and polyethers -Based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, carboxyl group by polyaddition reaction with a dialcohol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group Contains urethane resin.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems Propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride at the end of urethane resin by polyaddition reaction with alkylene oxide adduct diol, dialcohol compounds such as compounds having phenolic hydroxyl group and alcoholic hydroxyl group A terminal carboxyl group-containing urethane resin obtained by reacting a dibasic acid anhydride such as

  (4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( (Meth) acrylate or a part thereof modified with dibasic acid anhydrides such as propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, etc., carboxyl group-containing dialcohol compounds, and others Carboxyl group-containing photosensitive urethane resin by polyaddition reaction with a dialcohol compound.

  (5) During the synthesis of the resin described in (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, (Meth) acrylic carboxyl group-containing urethane resin.

  (6) During the synthesis of the resin described in (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as

  (8) A polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and the resulting hydroxyl group is subjected to phthalic anhydride or tetrahydroanhydride. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as phthalic acid or hexahydrophthalic anhydride is added.

  (9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenolic compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polybasic acid. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

  (10) One epoxy group and one or more (meth) acryloyl groups in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate are further added to the resins (1) to (9) described above. A carboxyl group-containing photosensitive resin obtained by adding a compound having the same.

  In addition, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.

  Since the carboxyl group-containing resin as described above has many free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution is possible.

  The acid value of such a carboxyl group-containing resin is preferably 40 to 200 mgKOH / g, more preferably 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, alkali development is performed satisfactorily. On the other hand, when it is 200 mgKOH / g or less, dissolution of the exposed portion by the developer is avoided, so that it is more than necessary. Lines do not fade or dissolution and peeling do not occur in the developer without distinction between exposed and unexposed areas, and normal resist patterns can be drawn.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin changes with resin frame | skeleton, generally 2,000-500,000 is preferable and it is more preferable in it being 4,000-350,000. When the weight average molecular weight is 2,000 or more, tack-free performance commensurate with practical use is obtained, the moisture resistance of the coated film after exposure is improved, and a cured product that is satisfactory in terms of resolution is obtained. On the other hand, when the weight average molecular weight is 500,000 or less, developability and storage stability are also improved.

  It is preferable that the compounding quantity of such carboxyl group-containing resin is 50-85 mass% in the whole composition, especially 60-70 mass%. When the blending amount is 50% by mass or more, the film strength is sufficient. On the other hand, by setting it as 85 mass% or less, the viscosity of a composition falls moderately and workability | operativity, such as applicability | paintability, becomes favorable.

  These carboxyl group-containing resins are not limited to those listed, and can be used singly or in combination.

  The phenolic hydroxyl group-containing resin includes a compound having a phenolic hydroxyl group, such as a compound having a biphenyl skeleton or a phenylene skeleton, or both, or a phenolic hydroxyl group-containing compound such as phenol, orthocresol, paracresol, meta Cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6 -Phenolic hydroxyl group-containing resins having various skeletons synthesized using dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol and the like may be used.

  For example, phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F, bisphenol S type phenol resin, poly-p-hydroxy Known and commonly used phenol resins such as a condensate of styrene, naphthol and aldehydes, or a condensate of dihydroxynaphthalene and aldehydes can be used.

  Commercially available products of such phenolic hydroxyl group-containing resins include HF-1, H-60 (Maywa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (Dai Nippon Printing Co., Ltd.), Vesmol CZ- 256-A (manufactured by DIC Corporation), Siyonol BRG-555, Siyonor BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Petrochemical Co., Ltd.), or polyvinylphenol CST70, CST90, S-1P And S-2P (manufactured by Maruzen Petrochemical Co., Ltd.). These phenolic hydroxyl group-containing resins can be used alone or in appropriate combination of two or more.

  As such a phenolic hydroxyl group-containing resin, materials other than those listed above can also be used, and the blending amount is preferably 15 to 35% by mass, particularly 20 to 30% by mass in the total composition. . When the blending amount is 15% by mass or more, the development is performed well, the Tg of the composition is increased, and the film strength is sufficient. On the other hand, by setting it as 35 mass% or less, the workability | operativity becomes favorable, without the viscosity of a composition falling too much.

  In the present invention, as the component (A), any one of a carboxyl group-containing resin and a phenolic hydroxyl group-containing resin, or a mixture thereof may be used.

  Among these, it is preferable to use a carboxyl group-containing resin from the viewpoint of developability.

[Component (B): at least one of a photobase generator and a photopolymerization initiator]
The composition of this invention contains at least 1 sort (s) of a photobase generator and a photoinitiator as a component (B).

  The photobase generator functions as a catalyst for the addition reaction between a polyimide resin having a carboxyl group and a thermosetting component when the molecular structure is changed by light irradiation such as ultraviolet light or visible light, or when the molecule is cleaved. It is a compound that produces one or more basic substances. Examples of basic substances include secondary amines and tertiary amines.

  Examples of photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alkoxyoxybenzyl carbamates. And compounds having a substituent such as a group. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferred. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable.

  In addition, examples of the photobase generator include carbamate derivatives and quaternary ammonium salts.

  Other photobase generators include WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2- propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate), and the like can also be used.

  Furthermore, a part of the photopolymerization initiator described later also functions as a photobase generator.

  As the photopolymerization initiator used in the present invention, any known photopolymerization initiator can be used, and among them, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, an acyl. A phosphine oxide photopolymerization initiator and a titanocene photopolymerization initiator are preferred.

  In addition, a photopolymerization initiator having a substituent such as an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alkoxybenzyl carbamate group can also be used. . These photopolymerization initiators will be described below.

  A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the oxime ester photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (Phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1 -[4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyl) Oxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) ) Phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime ) -1- [9-Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2 Butylbenzoyl) -9H-carbazol-3-yl] ethanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimino) -4- (4-chlorophenyl) Thio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone can be used, and as a commercial product, CGI-325 manufactured by BASF Japan Ltd. Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, and the like.

  In addition, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used, and specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (II). .

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換基を有していてもよい）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換基を有していてもよい）を表し、
Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換基を有していてもよい）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換基を有していてもよい）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、
Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、
ｎは０又は１の整数である）。

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group which may have a substituent, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, 1 to 1 carbon atoms). 8 may be substituted with an alkoxy group, an amino group, an alkylamino group having a C 1-8 alkyl group, or a dialkylamino group),
Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, or a phenyl group (an alkyl group having 1 to 17 carbon atoms, or 1 to 8 carbon atoms). An alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group which may have a substituent, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, a carbon number) 1-8 alkoxy group, amino group, alkylamino group having 1-8 carbon atoms or dialkylamino group may have a substituent), anthryl group, pyridyl group, benzofuryl group, benzothienyl Represents a group,
Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2 ′. -Represents styrene-diyl,
n is an integer of 0 or 1.

  In particular, in the above formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene. Photoinitiators are preferred.

  When the oxime ester photopolymerization initiator is used, the blending amount is 0.01 to 10 parts by weight, particularly 0.5 to 5 parts by weight with respect to 100 parts by weight of the (A) alkali-soluble resin. preferable. By setting the content to 0.01 parts by mass or more and 10 parts by mass or less, the coating film is stably formed, the coating film properties such as chemical resistance are maintained, and the light absorption on the surface of the solder resist coating film is kept constant. Sagging and deep part curability are considered good.

  Specific examples of the α-aminoacetophenone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -butane-1- ON, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucillin (registered trademark) TPO manufactured by BASF Japan, Irgacure 819 manufactured by BASF Japan, and the like.

  Each blending amount in the case of using an α-aminoacetophenone photopolymerization initiator or an acylphosphine oxide photopolymerization initiator is 0.01 to 15 parts by mass with respect to 100 parts by mass of (A) alkali-soluble resin, in particular. It is preferable that it is 0.5-10 mass parts. By setting the content to 0.01 parts by mass or more and 15 parts by mass or less, the coating film can be stably formed, the coating film characteristics such as chemical resistance can be maintained, and a sufficient outgas reduction effect can be obtained. Light absorption on the surface of the coating film is kept constant, and deep part curability is further improved.

  Specific examples of titanocene photopolymerization initiators include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, and bis (cyclopentadienyl) -bis. (2, 3, 4, 5, 6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium and the like. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

  The amount of the titanocene photopolymerization initiator used is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. Particularly preferred is 0.1 to 2 parts by mass. By setting the content to 0.05 parts by mass or more and 5 parts by mass or less, deep part curability is improved and there is no possibility of causing large halation.

  Specific examples of the photopolymerization initiator having an acyloxyimino group include O, O'-diacetphenone oxime succinate, O, O'-dinaphthophenone oxime succinate, benzophenone oxime acrylate-styrene copolymer, and the like. Can be mentioned.

  Specific examples of the photopolymerization initiator having an N-formylated aromatic amino group and an N-acylated aromatic amino group include, for example, di-N- (p-formylamino) diphenylmethane, di-N (p-acetate). Ethylamino) diphenylmelane, di-N- (p-benzoamido) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetyl Aminonaphthalene, 1,5-diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone 3,3′-dimethyl-4,4′-diformylaminobi Eniru, 4,4'-di-formyl-amino benzophenone.

  Examples of the photopolymerization initiator having a nitrobenzyl carbamate group or an alkoxybenzyl carbamate group include bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {{(2-nitrobenzyl) Oxy} toluylene, bis {{(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m-xylidine {{(2-nitro-4-chlorobenzyl) oxy} amide} and the like.

(Photoinitiator or sensitizer)
Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as a photopolymerization initiator in some cases, but are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

  Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.

  Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

  Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. .

  As the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4′-dimethylaminobenzophenone (manufactured by Nippon Soda Co., Ltd., Nissoure (registered trademark) MABP), 4 , 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin ) And other dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., Kayacure (registered trademark) EPA), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthetics, Quanta) ure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (International Bio-Synthetics, Quantacure BEA), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd., Kayacure DMBI) And 2-dimethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk). As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

  As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves It becomes possible to obtain a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by including a thioxanthone compound, it is possible to improve deep curability.

  As a compounding quantity in the case of using a photoinitiator adjuvant or a sensitizer, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of (A) alkali-soluble resin. When the blending amount of the photoinitiator assistant or sensitizer is less than 0.1 parts by mass, a sufficient sensitizing effect tends to be not obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts with respect to 100 mass parts of (A) alkali-soluble resin.

  The total amount of the photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

[Component (C): Thermosetting compound having an oxazolidone ring]
The composition of the present invention comprises a thermosetting compound having at least one oxazolidone ring and at least one glycidyl group as component (C).

  (C) The thermosetting compound having an oxazolidone ring is a compound having 1 to 4, preferably 2 oxazolidone rings, and 1 to 4 glycidyl groups, preferably 2 to 4 glycidyl groups. Is preferred.

（式中、ＸおよびＹは、酸素原子を有し、さらに窒素原子を有してもよい炭化水素基であり、ＸおよびＹの少なくとも一方は少なくとも１個のグリシジル基を有し、更に少なくとも１個のオキサゾリドン環を有してもよい）で表わされる化合物が成分（Ｃ）として用いられる。 That is, in the present invention, the following formula

(In the formula, X and Y are hydrocarbon groups having an oxygen atom and further having a nitrogen atom, and at least one of X and Y has at least one glycidyl group, and at least 1 The compound represented by the formula (which may have one oxazolidone ring) is used as component (C).

In the above, the hydrocarbon group is, for example, a linear group such as an alkyl group or an alkylene group, or an arylene such as phenylene, biphenylene, or bisphenol A, bisphenol F, bisphenol AF, bisphenol AC, bisphenol S, phenol novolac, cresol. It means a cyclic group containing a skeleton derived from at least one group selected from novolak.

で表わされる化合物が好ましく用いられる。 As component (C), in particular the following formula (IV)

The compound represented by is preferably used.

In the formula (IV), R ₁ is a divalent functional group which may have a substituent, particularly an alkylene group which may have a substituent, or an arylene group which may have a substituent. A divalent group derived from, for example, biphenylene, or a compound selected from bisphenol A, bisphenol F, bisphenol AF, bisphenol AC, bisphenol S, phenol novolac, cresol novolac, or combinations thereof, each having a substituent An alkylene group which may be substituted, an oxyalkylene group which may have a substituent, and an arylene group which may have a substituent (for example, a phenylene group or a naphthylene group). ), Preferably a biphenylene group, more preferably a 4,4′-biphenylene group, while R ₂ is a single bond or a divalent or higher functional group which may have a substituent, in particular a substituted An alkylene group which may have a group, an arylene group which may have a substituent, preferably a phenylene group or a toluylene group, more preferably a 1,4-phenylene group.

  In the above, the “alkyl group” represents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Among these, since the branched chain tends to have higher heat resistance than the straight chain, it is preferably an isopropyl group, an isobutyl group, or a tert-butyl group, and more preferably a tert-butyl group.

  The “alkylene group” means a divalent group derived by further removing one hydrogen atom at any position from the above-defined “alkyl group”, and has, for example, 1 to 6 carbon atoms, preferably 1 to 1 carbon atom. 4, In particular, methylene group, ethylene group, methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, trimethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group And a tetramethylene group, preferably a methylene group, an ethylene group, a methylethylene group, a 1,1-dimethylethylene group, a trimethylene group and the like.

  The “arylene group” of the arylene group is a divalent group derived from the above “aryl group” by further removing one hydrogen atom at an arbitrary position, preferably a group having 6 to 12 carbon atoms. Means.

  An optionally substituted group means an amino group, a nitro group, a carboxyl group or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group) , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group), aryl group, aralkyl group (for example, benzyl group, phenethyl group), alkoxy group (For example, methoxy group, ethoxy group) and the like may be further included.

  The weight average molecular weight of the (C) thermosetting compound having an oxazolidone ring of this embodiment is preferably 800 or more, more preferably 900 or more, and still more preferably 1000 or more. When the weight average molecular weight is 800 or more, the heat resistance of the cured product is increased, and at the same time, adhesion and toughness tend to be improved. Here, the weight average molecular weight refers to a value measured by gel permeation chromatography in terms of polystyrene.

  When the thermosetting compound which has (C) oxazolidone ring of this embodiment is an epoxy compound, Preferably an epoxy equivalent is 200-500, More preferably, it is 250-400. When the epoxy equivalent is 200 or more, the toughness increases, and when it is 500 or less, developability is maintained. Epoxy equivalent refers to a value measured by potentiometric titration according to JIS-K-7236.

The blending amount of the thermosetting compound having such (C) oxazolidone ring is:
The ratio of the reactive functional group (a) of the alkali-soluble resin to the functional group (b) of the thermosetting compound having the (C) oxazolidone ring is preferably (a) :( b) = 1: 1 to 1: 3, (A) :( b) = 1: 1 to 1: 2 is more preferable. By setting (a) :( b) = 1: 1 or more, the adhesion and toughness of the composition are improved, and by developing (a) :( b) = 1: 3 or less, the developability of the composition. Is maintained.

  The method for producing a thermosetting compound having an oxazolidone ring according to this embodiment is not particularly limited. For example, by reacting an isocyanate compound and a glycidyl compound having a biphenyl skeleton in the presence of an oxazolidone ring-forming catalyst. Can be obtained almost theoretically. The isocyanate compound and the glycidyl compound are preferably reacted in an equivalent ratio of 1: 2 to 1:10, whereby the heat resistance and water resistance of the cured epoxy resin are improved.

  In the present embodiment, as a raw material for obtaining a thermosetting compound having an oxazolidone ring, another glycidyl compound other than the glycidyl compound having a biphenyl skeleton may be used in combination. Specific examples thereof include dihydric phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, and tetrabromobisphenol A. 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxyphenyl) ethane, 4,4- [1- [4- [1- (4 Compounds obtained by glycidylating tris (glycidyloxyphenyl) alkanes such as -hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol; and novolacs such as phenol novolak, cresol novolak, and bisphenol A novolak Rishijiru of the compounds, and the like, but not particularly limited thereto.

Specific examples of the isocyanate compound used as the raw material include, for example, methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-1,3- Diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2, 2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10- Isocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω, ω′-1,3-dimethylbenzene diisocyanate, ω, ω′-1,4-dimethylbenzene diisocyanate, ω, ω′-1,3-dimethylcyclohexane diisocyanate, ω , Ω′-1,4-dimethylcyclohexane diisocyanate, ω, ω′-1,4-dimethylnaphthalene diisocyanate, ω, ω′-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1, 4-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene 2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, diphenyl ether-4,4′-diisocyanate, diphenyl ether-2,4′-diisocyanate, naphthalene-1, 4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4′-diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 2,3′-dimethoxybisphenyl-4,4′- Diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane-3,3′-diisocyanate, diphenylsulfite-4,4′- Diisocyanate, di Bifunctional isocyanate compounds such as Enirusurufon-4,4'-diisocyanate;
Polyfunctional isocyanate compounds such as polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate thiophosphate) -3,3 ′, 4,4′-diphenylmethane tetraisocyanate;
Examples include, but are not limited to, multimers such as dimers and trimers of the isocyanate compounds, blocked isocyanates masked with alcohol and phenol, and bisurethane compounds. Two or more of these isocyanate compounds may be used in combination.

  Among the above isocyanate compounds, a skeleton selected from a bifunctional or trifunctional isocyanate compound, more preferably a bifunctional isocyanate compound, more preferably isophorone, benzene, toluene, diphenylmethane, naphthalene, polymethylene polyphenylene polyphenyl, and hexamethylene. A bifunctional isocyanate compound having is preferably used. Use of these materials improves heat resistance and storage stability.

  In the present invention, in particular, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methylbenzene-2,4-diisocyanate (also known as tolylene-2,4-diisocyanate (2,4-TDI)), 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate (also known as tolylene-2,6-diisocyanate (2,6-TDI)), 1-methylbenzene-3,5 -Diisocyanates are preferably used.

As the oxazolidone ring-forming catalyst, any catalyst conventionally used for the same purpose can be used, and is not particularly limited.
Lithium compounds such as lithium chloride and butoxylithium; complex salts such as boron trifluoride;
Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetrabutylammonium bromide;
Tertiary amines such as dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine, N-methylmorpholine;
Phosphines such as triphenylphosphine;
Allyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, tetrabutylphosphonium acetate / acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium Phosphonium compounds such as iodide;
A combination of triphenylantimony and iodine;
Imidazoles such as 2-phenylimidazole and 2-methylimidazole;
Etc.

  In the present invention, a quaternary ammonium salt is preferably used as the oxazolidone ring-forming catalyst.

  These catalysts can be used individually by 1 type or in combination of 2 or more types.

  The amount used of the oxazolidone ring-forming catalyst is not particularly limited, and is usually used in the range of 5 ppm to 20000 ppm, preferably 10 ppm to 10000%, more preferably based on the total amount of glycidyl compound and isocyanate compound as raw materials. Is used in the range of 20 to 5000 ppm, more preferably 20 to 1000 ppm.

[Component (D): Block copolymer]
In the present invention, a block copolymer can be used as the additional component (D).

  (D) A block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by covalent bonds to form a long chain. What is solid in the range of 20 degreeC-30 degreeC is preferable. Any solid may be used within this range, and it may be solid even at a temperature outside this range. Due to being solid in the above temperature range, it is excellent in tackiness when formed into a dry film or applied to a substrate and temporarily dried.

As the block copolymer (D) used in the present invention, the following formula (I)
X-Y-X or X-Y-X '(I)
The block copolymer represented by these is preferable.

In the above formula, X or X ′ is a polymer unit (hard segment) having a glass transition point Tg of 0 ° C. or higher. Further, Y is a polymer unit (soft segment) having a glass transition point of less than 0 ° C. (hereinafter, these glass transition points are also expressed as Tg _{X / X ′} ≧ 0 ° C. and Tg _Y <0 ° C., respectively).

  Here, the (D) block copolymer generally means a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain. By using said (D) block copolymer, toughness is given to the hardened | cured material obtained from the curable resin composition of this invention.

The glass transition point of each polymer unit is particularly preferably −80 ° C. <Tg _y <0 ° C. and 0 ° C. ≦ Tg _{X / X ′} <150 ° C.

  Moreover, among the (D) block copolymers containing the structure of the formula (I), X and X ′ are highly compatible with the above-mentioned (A) alkali-soluble resin, and Y is Those having low compatibility are preferred, whereby a curable composition having desired toughness can be obtained.

X and X ′ in the formula (I) are (C ₁ -C ₃ alkyl) methacrylate such as polymethyl methacrylate (PMMA (Tg _x : 140 ° C.)), polystyrene (PS) (Tg _x : 100 ° C.), etc. Y is preferably poly (C ₁ -C ₆ alkyl) acrylate such as poly n-butyl acrylate (PBA) (Tg _y : −40 ° C.), C ₄ such as polybutadiene (PB) (Tg _y : −70 ° C.), etc. -C ₆ diene is preferred.

  The block copolymer (D) used in the present invention is preferably a terpolymer or more block copolymer, and a block copolymer with a precisely controlled molecular structure synthesized by a living polymerization method is effective for the present invention. It is more preferable in obtaining. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit have been clarified. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.

  (D) As a manufacturing method of a block copolymer, the method as described in a special table 2005-515281 and a special table 2007-516326 is mentioned, for example.

Examples of commercially available (D) block copolymers that can be applied to the present invention include acrylic triblock copolymers manufactured using living polymerization manufactured by Arkema Co., Ltd. As specific examples, polystyrene (Tg _x1 : 100 ° C)-polybutadiene (Tg _y : -70 ° C)-SBM type represented by polymethyl methacrylate (Tg _x2 : 140 ° C), polymethyl methacrylate (Tg _x1 : 140 ° C.)-MAM type represented by poly n-butyl acrylate (Tg _y : -40 ° C.)-Polymethyl methacrylate (Tg _x2 : 140 ° C.), and MAM N modified with carboxylic acid modification or hydrophilic group modification Type and MAM A type. The SBM type includes E41, E40, E21, E20, the MAM type includes M51, M52, M53, M22, SM6290XD30, the MAM N type includes 52N, 22N, and the MAM A type includes SM4032XM10. Is mentioned.

  It is also possible to use a block copolymer derived from methyl methacrylate and butyl acrylate such as Kuraray's clarity. Commercially available products include LA1114, LA2250, LA2140e, LA2330, and the like.

  (D) The weight average molecular weight of the block copolymer is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, and even more preferably 50,000 to 300,000. When the weight average molecular weight is 10,000 or more, the intended toughness can be obtained.

  On the other hand, when the weight average molecular weight is 500,000 or less, the viscosity of the curable resin composition becomes appropriate, and the printability and developability become good.

  The blending amount of the (D) block copolymer is preferably 0.5 to 30% by mass with respect to the total solid weight of the (A) alkali-soluble resin and (C) the thermosetting compound having an oxazolidone ring. -20% is more preferable. If it is 0.5% by mass or more, improvement in crack resistance can be expected, and if it is 30% by mass or less, it is preferable because developability and coating property can be maintained as a curable resin composition.

  In the present invention, particularly excellent toughness can be imparted to the cured product obtained from the curable resin composition of the present invention by using a block copolymer containing the structure of the above formula (I). It is said. The cured product of the present invention maintains the toughness of the resist by including a block copolymer containing the structure of the above formula (I) even when applied as a resist, and a step of patterning as a resist by development. Therefore, even in the harsh application environment as an alkali development or a solder resist, the generation of cracks and the progress of cracks are difficult, and the substrate is well protected.

  In particular, by setting the curing temperature of the composition to a temperature equal to or higher than the Tg of the hard segment, a resist having excellent toughness can be obtained.

  Furthermore, it is preferable that the curable resin composition of this invention contains (E) reactive diluent.

[Component (E): Reactive Diluent]
In the curable resin composition of the present invention, (E) a reactive diluent can be used. In particular, when the curable resin composition is a photosensitive curable resin composition, it is preferable in terms of curability and development resistance. The reactive diluent in the present invention is a compound having an ethylenically unsaturated group in the molecule, and is used for adjusting the viscosity of the curable resin composition, promoting curability and improving developability.

  As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide , N-methylolacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate, or their ethylene oxide adducts, propylene oxide adducts Or polyhydric acrylates such as ε-caprolactone adduct; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyacid acrylates of sidyl ether; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of each methacrylate corresponding to the acrylate.

  Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. The epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned. Such an epoxy acrylate resin can improve curability without deteriorating the touch drying property.

  In the present invention, when the reactive diluent (E) is used, one kind may be used alone, or two or more kinds may be used in combination.

  5-100 mass parts is preferable with respect to 100 mass parts of said (A) alkali-soluble resin, and, as for the compounding quantity of the above reactive diluents, 5-30 mass parts is more preferable. When the amount is 5 parts by mass or more, the surface curability is improved and damage to the exposed part is reduced during alkali development. On the other hand, when the amount is 100 parts by mass or less, good resolution without halation can be obtained while maintaining solubility in a dilute aqueous alkali solution.

[Thermosetting compound]
In the present invention, in addition to the above components, thermosetting compounds other than the above (C) can be used. As specific examples, it is preferable to use an epoxy compound or a polyfunctional oxetane compound other than the above, that is, an epoxy compound having no oxazolidone ring. Among these, an epoxy resin is preferably used.

  As the epoxy compound, liquid, crystalline low molecular weight, semi-solid, and solid materials can be used. As specific examples, the epoxy resin is a resin having an epoxy group, and any known one can be used. Can be used. Examples include polyfunctional epoxy resins having two or more epoxy groups in the molecule. In addition, a hydrogenated bifunctional epoxy compound may be used.

  Polyfunctional epoxy compounds include bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic ring Epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixtures thereof, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy Resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, epoxy resin having dicyclopentadiene skeleton, glycidyl meta Acrylate copolymer epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and a CTBN modified epoxy resin.

  Other liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3 ′, 4′-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, and (3 ′, 4′-epoxy-6′-methyl). And alicyclic epoxy resins such as (cyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate.

  As the epoxy compound, a commercially available product can be used. For example, HP4032 (manufactured by DIC, naphthalene type bifunctional epoxy resin, Tg: −5 ° C.), NC3000H, NC3000L (manufactured by Nippon Kayaku Co., Ltd., biphenyl type epoxy compound) , Tg: 20 ° C., 30 ° C. in order, EPPN501H (manufactured by Nippon Kayaku Co., Ltd., triphenylglycidyl ether type epoxy resin, Tg: 20 ° C.), jER828, jER834, jER1001 (Mitsubishi Chemical Corporation, in order liquid, semi-solid, Solid bisphenol A type epoxy resin, in order Tg: -20 ° C, 0 ° C, 30 ° C), DEN431, DEN438 (manufactured by Dow Chemical Co., epoxy novolac resin, in order Tg: -10 ° C, 0 ° C), P201 (Nippon Kayaku) Phenol novolac epoxy resin, Tg: 5 ° C., N870 (manufactured by DIC, modified A novolak-type resin, Tg: 20 ° C.).

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Here, it is preferable that the heat-reactive component has a benzene skeleton because heat resistance is improved. Moreover, when a thermosetting resin composition contains a white pigment, it is preferable that a thermoreactive component is an alicyclic skeleton. Thereby, photoreactivity can be improved.

  You may use a heat-reactive component 1 type or in combination of 2 or more types.

[Thermosetting catalyst]
In the present invention, it is preferable to use a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl. Imidazole derivatives such as 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4- Use amine compounds such as methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, etc. But Kill.

  Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited to these, as long as it is a thermosetting catalyst for epoxy compounds or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.

  Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.

  The blending amount of these thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the thermosetting compound (other than component (C)). It is. In the case of 0.1 mass part or more, the reactivity of a thermosetting component improves and it can anticipate the improvement of Tg and the fall of CTE. On the other hand, in the case of 20 parts by mass or less, developability can be maintained.

[Other optional ingredients]
The curable composition of the present invention further includes at least one of a chain transfer agent, an adhesion promoter, an antioxidant, a rust inhibitor, a polymerization inhibitor, an ultraviolet absorber, a thickener, an antifoaming agent, and a leveling agent, Components such as a silane coupling agent, a filler, a binder, a flame retardant, a thixotropic agent, and a rust inhibitor can be blended. As these, those known in the field of electronic materials can be used.

  Furthermore, the curable resin composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to the substrate.

  The curable resin composition of this invention can also be made into the form of the dry film provided with the support body (carrier film etc.) and the layer which consists of the said curable resin composition formed on the support body.

  In forming a dry film, the curable resin composition of the present invention is diluted with an organic solvent to adjust to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is a film thickness after drying, 5-150 micrometers, Preferably it selects suitably in the range of 10-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After forming the curable resin composition of the present invention on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.

  As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain A tack-free coating film can be formed by coating by a method such as a coating method and volatilizing and drying (temporary drying) an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Further, in the case of a dry film obtained by applying the above composition on a carrier film and drying and winding it as a film, after laminating the curable resin composition layer on the substrate with a laminator or the like The resin insulating layer can be formed by peeling off the carrier film.

  The curable composition of the present invention can be suitably used as various resists or insulating materials for forming a pattern layer of a printed wiring board, and is particularly useful as a material for a solder resist or an interlayer insulating layer.

  The curable resin composition of the present invention can be subjected to pattern formation / curing by screen printing on a substrate or pattern-shaped light irradiation.

In the pattern forming method using the curable composition of the present invention,
Applying a curable composition on a substrate (a),
A step (b) of activating the photopolymerization initiator contained in the curable composition by pattern-shaped light irradiation to cure the light-irradiated part, and a negative pattern layer by removing the unirradiated part by development. A negative pattern is formed by the forming step (c).

[Step (a): Composition layer forming step]
The said process (a) is a process of forming the composition layer which consists of a curable composition in a base material. The method of forming the composition layer can be based on a method of applying and drying a liquid curable composition on a substrate, or a method of laminating a curable composition in a dry film on a substrate. .

  As a method for applying the curable composition to the substrate, known methods such as a blade coater, a lip coater, a comma coater, and a film coater can be appropriately employed. Also, the drying method is a method using a hot-air circulation type drying furnace, IR furnace, hot plate, convection oven, etc., equipped with a heat source of the heating method by steam, and the hot air in the dryer is counter-contacted and supported by the nozzle Known methods such as a method of spraying on the body can be applied.

  As the substrate, in addition to a printed wiring substrate and a flexible printed wiring substrate in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy Copper-clad laminates of all grades (FR-4 etc.) using composite materials such as resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate ester Polyimide film, PET film, glass substrate, ceramic substrate, wafer substrate and the like can be used.

  Volatile drying performed after the application of the curable resin composition of the present invention is performed by using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like (with a steam-heated air source). Can be carried out by using a counter-current contact method and a method of spraying a nozzle on a support.

[Step (b): Curing step]
In the step (b), patterning is performed by evaporating and drying the solvent after the step (a) and exposing the coating film obtained (irradiation with active energy rays, particularly light such as ultraviolet rays). As one aspect (b-1), the photopolymerization initiator in the curable resin composition sequentially reacts with the ethylenically unsaturated double bond, thereby causing light exposure by an exposed part (active energy rays, particularly ultraviolet rays). The irradiated part is cured. In the case of such an embodiment, it is possible to form a negative pattern with respect to the alkaline developer, and it is preferable from the viewpoint that the curability is improved by performing thermosetting together.

  Further, in such an embodiment, the exposure is selectively carried out by the active energy rays or directly by the direct drawing apparatus through the photomask on which the pattern is formed by the contact method (or the non-contact method). Thereby, a photoirradiation part is hardened because the photobase generation component contained in the curable composition of an exposure part generates a base.

  Moreover, as another aspect (b-2), light irradiation is performed when the light irradiation part hardens | cures by activating the photoinitiator contained in a curable composition by irradiating light in a negative pattern shape. The base generated in the part destabilizes the photopolymerization initiator, and further, the base is generated and proliferated, so that the deep part of the light irradiation part is sufficiently cured.

  As the light irradiator used for light irradiation, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser using CAD data from a computer), a light irradiator equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp It is possible to use a light irradiator mounted, a light irradiator equipped with a mercury short arc lamp, an ultraviolet lamp such as a (super) high pressure mercury lamp, or a direct drawing device using LEDs.

As the active energy ray, it is preferable to use laser light or scattered light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, the photoreactivity of the curable composition can be improved efficiently. As long as this range is used, in the case of laser light, either a gas laser or a solid laser may be used. Moreover, the light irradiation amount varies depending on the film thickness, etc., generally 100~1500mJ / cm ^2, preferably be in the range of 300~1500mJ / cm ^2.

  Note that a negative mask can be used as the patterned light irradiation mask.

  In the step (b), when the light irradiation part is cured by activating the photopolymerization initiator contained in the curable composition by light irradiation in the form of b-2, that is, a negative pattern. When the photopolymerization initiator is destabilized by the base generated in the light irradiation part, and further the base is generated and proliferated to sufficiently cure the deep part of the light irradiation part, the light irradiation part is further cured by heating. Is preferred (PEB: Post Exposure Bake). Thereby, it can harden | cure to a deep part from the base which generate | occur | produced at the process (b) carries out an addition reaction with respect to a thermosetting component.

  However, in the case of providing a small-diameter opening having a 50 μm level in patterning, halation or undercut does not occur in the opening and the resolution is improved when the PEB process is not performed.

  In the curable composition, the heating temperature is preferably a temperature at which the light-irradiated portion is thermally cured after the light irradiation, but the non-irradiated portion is not thermally cured.

  For example, it is preferable to heat at a temperature lower than the heat generation start temperature or heat generation peak temperature of the unirradiated curable composition and higher than the heat generation start temperature or heat generation peak temperature of the light irradiated curable composition. By heating in this way, only the light irradiation part can be selectively cured.

  Here, heating temperature is 40-140 degreeC, for example, Preferably it is 60-120 degreeC. By setting the heating temperature to 40 ° C. or higher, the light irradiation part can be sufficiently cured. On the other hand, by setting the heating temperature to 140 ° C. or lower, only the light irradiation part can be selectively cured. The heating time is, for example, 1 to 120 minutes, preferably 10 to 80 minutes. The heating method is the same as the drying method.

  In the unirradiated portion, no base is generated from the photopolymerization initiator, so that thermosetting is suppressed.

[Step (c): Development step]
Step (c) is a step of forming a negative pattern layer by removing unirradiated portions by development. As a developing method, a known method such as a dipping method, a shower method, a spray method, or a brush method can be used. As a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid can be used. An amine such as sodium, ammonia or ethanolamine, an alkali aqueous solution such as tetramethylammonium hydroxide aqueous solution (TMAH) or a mixture thereof can be used.

  In consideration of the environment, the resin composition of the present invention is preferably developable with a developer having a pH of less than 12.

[Step (d)]
It is preferable that the said pattern formation method includes the further light irradiation process (d) after a process (c). By performing light irradiation such as ultraviolet irradiation after the step (c), photoreactive components such as reactive diluent remaining without reacting at the time of exposure can be reacted. The wavelength of irradiation light and the light irradiation amount (exposure amount) in the light irradiation step (d) may be the same as or different from those in the step (b). A suitable light irradiation amount (exposure amount) is 150 to 2000 mJ / cm ² .

[Step (e)]
The pattern forming method preferably further includes a thermosetting (post-cure) step (e) after the step (c).

  When both the step (d) and the step (e) are performed after the step (c), the step (e) is preferably performed after the step (d), but may be performed before the step (d).

  In the step (e), the pattern layer is sufficiently heat-cured by the base generated from the photopolymerization initiator in the step (b) or the steps (b) and (d). Since the unirradiated part has already been removed at the time of the step (e), the step (e) can be performed at a temperature equal to or higher than the curing reaction start temperature of the unirradiated curable composition. Thereby, a pattern layer can fully be thermosetted. The heating temperature is, for example, 150 ° C. or higher.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited to these Examples. In the following, “part” and “%” are based on mass unless otherwise specified.

[Examples 1 to 20 and Comparative Examples 1 to 4]
<Preparation of curable composition>
In accordance with the formulation described in Table 1-1 to Table 1-3 below, the materials of Examples 1 to 20 and Comparative Examples 1 to 4 were blended, and each of the examples and comparative examples was premixed with a stirrer. A curable resin composition was prepared.

  In addition, the thermosetting compounds A to C having (A) alkali-soluble resins 1 to 3 and (C) oxazolidone rings used in Examples and Comparative Examples were synthesized as follows. Details of the other components are added below Table 1-3.

<Example of synthesis of alkali-soluble resin>
Synthesis of alkali-soluble resin 1:
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolac type cresol resin (Showa Denko KK, Shonor CRG951, OH equivalent: 119.4), hydroxylation 1.19 parts of potassium and 119.4 parts of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised by heating.

Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours.

  Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

  293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reactor equipped with a meter and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring.

  12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene.

  Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water.

  Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate) with an evaporator to obtain a novolak acrylate resin solution.

  Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. After cooling, the solid had an acid value of 88 mg KOH / g and a solid content of 65% containing a carboxyl group Resin 1 was obtained.

Synthesis of alkali-soluble resin 2:
A flask equipped with a condenser and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin, and kept at a temperature of 40 ° C. or lower, and 228 parts of 25% aqueous sodium hydroxide solution was added. The reaction was carried out at 0 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ° C. or lower. Thereafter, the mixture was allowed to stand to separate the aqueous layer. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and then washed three times with 500 parts of distilled water, and water, solvent, and the like were removed under reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.

  When a part of the methanol solution of the obtained polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.

  500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and dissolved uniformly at 50 ° C. After dissolving uniformly, methanol was removed under reduced pressure at a temperature of 50 ° C. or lower. Thereafter, 8 parts of oxalic acid was added and reacted at 100 ° C. for 10 hours. After completion of the reaction, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 550 parts of novolak resin A.

Furthermore, in an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 130 parts of the above-mentioned novolak resin A, 2.6 parts of 50% aqueous sodium hydroxide solution, toluene / methyl isobutyl ketone (mass ratio) = 2/1) 100 parts were charged, and the system was purged with nitrogen while stirring. Next, the temperature was raised by heating, and 45 parts of ethylene oxide was gradually introduced and reacted at 150 ° C. and 8 kg / cm ² . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator. The hydroxyl value was 175 g / eq. An ethylene oxide adduct of novolak resin A was obtained. This was an average of 1 mole of ethylene oxide added per equivalent of phenolic hydroxyl group.

  175 parts of the ethylene oxide adduct of the novolak resin A thus obtained, 50 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, 130 parts of toluene, a stirrer, thermometer, air A reactor equipped with a blowing tube was charged, stirred while blowing air, heated to 115 ° C., and reacted for another 4 hours while distilling off the water produced by the reaction as an azeotrope with toluene. Cooled to room temperature. The obtained reaction solution was washed with 5% NaCl aqueous solution and toluene was removed by distillation under reduced pressure. Diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a nonvolatile content of 68%.

  Next, 312 parts of the resulting acrylate resin solution, 0.1 part of hydroquinone monomethyl ether and 0.3 part of triphenylphosphine were charged into a four-necked flask equipped with a stirrer and a reflux condenser, and this mixture was charged at 110 ° C. Then, 45 parts of tetrahydrophthalic anhydride was added and reacted for 4 hours. After cooling, a carboxyl group-containing resin 2 having a nonvolatile content of 72% and a solid content acid value of 65 mgKOH / g was obtained.

Synthesis of alkali-soluble resin 3:
A four-necked flask equipped with a stirrer and a reflux condenser was charged with 210 parts of a cresol novolac type epoxy resin (manufactured by DIC Corporation, “Epicron” (registered trademark) N-680, epoxy equivalent: 210). 96.4 parts of tall acetate was added and dissolved by heating. Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was allowed to react for about 16 hours until the acid value became 3.0 mgKOH / g or less.

  The reaction product was cooled to 80 to 90 ° C., 76 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the carboxyl group-containing resin 3 having a solid acid value of 78 mgKOH / g and a nonvolatile content of 65% was obtained. Got.

<(C) Synthesis Example of Thermosetting Compound Having Oxazolidone Ring>
Synthesis of thermosetting compound A having an oxazolidone ring:
In the reactor, 100 parts by mass of a biphenyl type epoxy resin (trade name: YX4000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185 g / eq) and tetrabutylammonium bromide (trade name: tetra-n-butylammonium bromide) 0.04 part by mass, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred and heated to adjust the internal temperature to 175 ° C. Furthermore, 11.8 parts by mass of tolylene diisocyanate (trade name: Coronate T80 (registered trademark), manufactured by Nippon Polyurethane Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 90 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain a reaction product represented by the formula (IV).

As a result of IR measurement of the reaction product, peaks were observed at 1750 cm ⁻¹ and 910 cm ⁻¹ , and it was confirmed that the reaction product contained an oxazolidone ring and an epoxy group. Furthermore, when the epoxy equivalent of the said reaction product was measured, the measured value 250g / eq was calculated | required (production | generation of the thermosetting compound A which has an oxazolidone ring).

Synthesis of thermosetting compound B having an oxazolidone ring:
In the reactor, 100 parts by mass of a biphenyl type epoxy resin (trade name: YX4000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185 g / eq) and tetrabutylammonium bromide (trade name: tetra-n-butylammonium bromide) 0.04 part by mass, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred and heated to adjust the internal temperature to 175 ° C. Furthermore, 11.8 parts by mass of tolylene diisocyanate (trade name: Coronate T80 (registered trademark), manufactured by Nippon Polyurethane Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 90 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain a reaction product represented by the formula (IV).

As a result of IR measurement of the reaction product, peaks were observed at 1750 cm ⁻¹ and 910 cm ⁻¹ , and it was confirmed that the reaction product contained an oxazolidone ring and an epoxy group. Furthermore, when the epoxy equivalent of the said reaction product was measured, the measured value 292g / eq was calculated | required (production | generation of the thermosetting compound B which has an oxazolidone ring).

Synthesis of thermosetting compound C having an oxazolidone ring:
In the reactor, 100 parts by mass of a biphenyl type epoxy resin (trade name: YX4000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185 g / eq) and tetrabutylammonium bromide (trade name: tetra-n-butylammonium bromide) 0.04 part by mass, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred and heated to adjust the internal temperature to 175 ° C. Furthermore, 11.8 parts by mass of tolylene diisocyanate (trade name: Coronate T80 (registered trademark), manufactured by Nippon Polyurethane Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 90 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 15 hours to obtain a reaction product represented by the formula (IV).

As a result of IR measurement of the reaction product, peaks were observed at 1750 cm ⁻¹ and 910 cm ⁻¹ , and it was confirmed that the reaction product contained an oxazolidone ring and an epoxy group. Furthermore, when the epoxy equivalent of the said reaction product was measured, measured value 395g / eq was calculated | required (production | generation of the thermosetting compound C which has an oxazolidone ring).

  Regarding all the obtained curable resin compositions, the following 1. ~ 6. The test was conducted.

<1. Evaluation of Glass Transition Point (Tg) and Linear Expansion Coefficient (CTEα1)>
On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 μm. This was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. On the other hand, exposure was performed with a strip-shaped negative mask of 50 mm × 3 mm at an optimal exposure (1000 mJ / cm ² ) using an HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, 1 wt. Development was performed by spraying a 120% aqueous sodium carbonate solution under a spray pressure of 0.2 MPa for 120 seconds to obtain a pattern layer of a cured coating. Further, the pattern layer was cured by heating at 150 ° C. for 60 minutes.

  The cured film of the evaluation board | substrate obtained by the above was peeled off from copper foil, and evaluation was implemented.

  The measurement was performed using a TMA measuring apparatus (Shimadzu Corporation model name: TMA / SS6000), and Tg and CTEα1 (linear expansion coefficient) (0 ° C.-50 ° C.) were evaluated. The evaluation criteria are as follows.

Evaluation criteria for Tg ◎… 140 ° C. or higher ○… 135 ° C. or higher and lower than 140 ° C. Δ ... 125 ° C. or higher and lower than 135 ° C.

Evaluation criteria for CTE α1 ◎… less than 50 ppm ○… 50 ppm or more and less than 60 ppm ×… 60 ppm or more

<2. Evaluation of resolution>
The plated copper substrate is roughened using CZ8101 at an etching rate of 1 μm, and the entire surface of the roughened substrate is screen-printed so that the dry film thickness is about 20 μm. Applied. This was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. On the other hand, pattern exposure was performed with an optimum exposure (1000 mJ / cm ² ) using ORC HMW680GW (metal halide lamp, scattered light). Thereafter, 1 wt. Development was performed by spraying a 60% aqueous sodium carbonate solution under a spray pressure of 0.2 MPa for 60 seconds to obtain a pattern layer of a cured film. Further, the pattern layer was cured by heating at 150 ° C. for 60 minutes.

  The opening diameter of the evaluation substrate obtained as described above was observed, and it was observed whether halation and undercut were generated for each diameter. Hereinafter, in the observation result, a case where neither halation nor undercut occurs is defined as “good”.

◎ ... Good opening formation with a diameter of 50 μm ○ ... Good opening formation with a diameter of 70 μm △ ... Good opening formation with a diameter of 100 μm × ...

<3. Adhesion evaluation>
18 μm copper foil was roughened with CZ8101 at an etching rate of (i) 0.7 μm and (ii) 1 μm, respectively, and the curable resin composition was screen-printed on the roughened copper foil surface to dry film The entire surface was coated to a thickness of about 40 μm.

  Further, the entire surface of the curable resin composition was applied to polyimide (Kapton (registered trademark)) so as to have a dry film thickness of about 40 μm by screen printing.

The applied curable resin composition was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature, thereby forming a resin layer made of the curable resin composition. On the other hand, whole surface exposure was performed with an optimum exposure (1000 mJ / cm ² ) using ORC HMW680GW (metal halide lamp, scattered light). Thereafter, 1 wt. Development was performed by spraying a 60% aqueous sodium carbonate solution under a spray pressure of 0.2 MPa for 60 seconds to obtain a pattern layer of a cured film. Further, the pattern layer was cured by heating at 150 ° C. for 60 minutes. Both the sample having the copper foil and the sample having polyimide were used as evaluation boards.

  A two-component epoxy adhesive (Araldite) was applied to the composition side of the evaluation substrate after curing, and an etch-out substrate was laminated thereon.

  After the epoxy adhesive was cured, the copper foil adhered to the insulating layer was cut out with a width of 1 cm and subjected to a 90-degree peel test according to JIS K6854-1. Peel strength was measured using a peel gauge.

A: Peel strength of 6 N / m ² or more.
○: Peel strength of 5 N / m ² or more and less than 6 N / m ² .
Δ: Peel strength 4 N / m ² or more and less than 5 N / m ² .
X: Peel strength of less than 4 N / m ²

<4. Evaluation of toughness>
On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 μm. This was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. On the other hand, exposure was performed in a state where a strip-shaped negative mask of 80 mm × 10 mm was applied at an optimum exposure amount (1000 mJ / cm ² ) by using HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, 1 wt. Development was performed by spraying a 90% aqueous sodium carbonate solution under a spray pressure of 0.2 MPa for 90 seconds to obtain a pattern layer of a cured coating. Further, the pattern layer was cured by heating at 150 ° C. for 60 minutes.

  The cured film of the evaluation board | substrate obtained by the above was peeled off from copper foil, and evaluation was implemented. The measurement was performed using a tensile testing machine (Shimadzu Corporation model name: AGS-G 100N), and the elongation at break was evaluated. The evaluation criteria are as follows.

◎ ... Elongation at break 6% or more ○ ... Elongation at break 4% or more and less than 6% △ Elongation at break 2% or more and less than 4% × ... Elongation at break 2% or less

<5. TCT (thermal cycle test) resistance>
A curable resin composition was applied to the entire surface of the substrate on which a 2 mm copper line pattern was formed by screen printing so as to have a dry film thickness of about 20 μm. This was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. On the other hand, exposure was performed in a state where a negative mask of a 3 mm square resist pattern was applied on a copper line at an optimal exposure amount (1000 mJ / cm ² ) by ORC HMW680GW (metal halide lamp, scattered light). .

Thereafter, 1 wt. Development was performed by spraying a 90% aqueous sodium carbonate solution under a spray pressure of 0.2 MPa for 90 seconds to obtain a pattern layer of a cured coating. Further, the pattern layer was cured by heating at 150 ° C. for 60 minutes.

  The evaluation board | substrate obtained by the above was put into the thermal cycle machine by which the temperature cycle of -40 degreeC-120 degreeC is set cyclically, and TCT was performed. And the external appearance of the evaluation board | substrate at the time of 500 cycles, 800 cycles, and 1000 cycles was observed visually. The evaluation criteria are as follows.

◎: No abnormality at 1000 cycles ○: No abnormality at 800 cycles, crack generation at 1000 cycles △: No abnormality at 500 cycles, crack generation at 800 cycles ×: Crack generation at 500 cycles

<6. Electrical characteristics (insulation resistance) measurement>
The entire surface of the curable resin composition was applied to the comb-shaped electrode B coupon of the IPC B-25 test pattern so as to have a dry film thickness of about 20 μm by screen printing. This was dried at 80 ° C. for 30 minutes and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. On the other hand, exposure was performed in a state where a strip-shaped negative mask of 80 mm × 10 mm was applied at an optimum exposure amount (1000 mJ / cm ² ) by using HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, 1 wt. Development was performed by spraying a 90% aqueous sodium carbonate solution for 90 seconds under the condition of a spray pressure of 0.2 MPa to obtain a pattern layer of a cured coating. Further, the pattern layer was cured by heating at 150 ° C. for 60 minutes.

  A bias voltage of DC 100 V was applied to the comb-shaped electrode of the evaluation substrate obtained as described above, and 85 ° C., 85% R.D. H. The insulation resistance value after 1,000 hours was measured in a constant temperature and humidity chamber.

  The components described in the table are as follows.

Alkali-soluble resin 4: HF-1 (phenol novolak resin (Maywa Kasei Co., Ltd.) dissolved in cyclohexanone (solid content 60%)
IrgOXE02: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), manufactured by BASF Japan Ltd. WPBG-0018: 9-An Trilmethyl-N, N′-diethylcarbamate), Irg907 manufactured by Wako Pure Chemical Industries, Ltd .: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, lucillin manufactured by BASF Japan Ltd. (Registered trademark) TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Japan Ltd. jER828: Bis-A type liquid epoxy resin, manufactured by Mitsubishi Chemical Corporation DEN431: epoxy novolac resin, The Dow・ Made by Chemical Company
M52NDPM50: Block copolymerized polyacrylic acid resin, Nanostrength M52N (XYX type (containing acrylamide), Mw = 100,000, manufactured by Arkema Co., Ltd.) dissolved in DPM, solid content 50%.

  M53DPM30: A block copolymerized polyacrylic acid resin, Nanostrength M53 (XY type (containing no acrylamide), Mw = 100,000 to 300,000, manufactured by Arkema Corporation) is dissolved in dipropylene glycol monomethyl ether (DPM), Solid content 30%.

  M53GDPM30: block copolymerized polyacrylic acid resin, nano-strength M53G (XYX ′ type (not containing acrylamide, containing 10% glycidyl methacrylate (GMA) with respect to polymethyl methacrylate (PMMA)), Mw = 100,000 ~ 300,000, manufactured by Arkema Co., Ltd.) with DPM, solid content 30%.

Epolide PB3600: Epoxidized polybutadiene, manufactured by Daicel Corporation KAYARAD DPHA: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. 2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.

As shown in the above table, in all examples, the glass transition point (Tg), linear expansion coefficient (CTEα1), resolution, adhesion, toughness, TCT (thermal cycle test) resistance, electrical characteristics (insulation) It was confirmed that all the characteristics of the resistance value were excellent in good balance. In contrast, Comparative Examples 1 and 2 that do not contain (C) a thermosetting compound having an oxazolidone ring have poor adhesion to copper and polyimide, and the Comparative Example has a low glass transition point (Tg) and a linear expansion coefficient ( It was confirmed that CTEα1) was high.
Further, unlike Examples 1 to 15 and Comparative Examples 1 and 2, in Examples 16 to 20 and Comparative Examples 3 and 4, (D) block copolymer was added to each composition. (D) In Examples 16 to 20 including a block copolymer, it was confirmed that TCT resistance was consistently improved.

Claims (10)

(A) an alkali-soluble resin,
(B) a photobase generator, and at least one of photopolymerization initiators, and (C) a thermosetting compound having an oxazolidone ring,
Contain,
The thermosetting compound having the (C) oxazolidone ring is represented by the following formula (IV):

(In the formula, R ₁ represents a divalent functional group which may have a substituent, and R ₂ represents a single bond or a divalent or higher functional group which may have a substituent. .)
A curable resin composition characterized by being represented by the formula:   Furthermore, (D) block copolymer is contained, The curable resin composition of Claim 1 characterized by the above-mentioned. The (D) block copolymer is represented by the following formula (I)

X-Y-X or X-Y-X '(I)

(In the formula, X or X ′ is a polymer unit having a glass transition point Tg of 0 ° C. or more, and Y is a polymer unit having a glass transition point Tg of less than 0 ° C.)
It is represented by these. The curable resin composition of Claim 2 characterized by the above-mentioned. 4. The curable resin composition according to claim 3 , wherein a polar group is contained in X or X ′ of the (D) block copolymer.   The weight average molecular weight of said (D) block copolymer is 10,000-500,000, The curable resin composition of any one of Claims 2-4 characterized by the above-mentioned.   The curable resin composition according to any one of claims 1 to 5, wherein the (A) alkali-soluble resin is at least one of a carboxyl group-containing resin and a phenolic hydroxyl group-containing resin.   Furthermore, (E) a reactive diluent is included, The curable resin composition of any one of Claims 1-6 characterized by the above-mentioned.   A dry film obtained by applying and drying the curable resin composition according to any one of claims 1 to 7 on a film. The cured product of the curable composition is a curable resin composition monomers other according to any one constituting the dry film according to claim 8 of claims 1-7.   A printed wiring board comprising the cured product according to claim 9.